Journal of Environmental Management 250 (2019) 109457

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Journal of Environmental Management

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Research article

Adsorption of CO2 on KOH activated carbon adsorbents: Effect of different T

mass ratios
Jasminder Singha, Haripada Bhuniab,∗∗, Soumen Basua,∗
a
School of Chemistry and Biochemistry, Thapar Institute of Engineering & Technology, (Deemed to be University), Patiala, 147004, Punjab, India
b
Department of Chemical Engineering, Thapar Institute of Engineering & Technology (Deemed to be University), Patiala, 147004, Punjab, India

A R T I C LE I N FO A B S T R A C T

Keywords: Nitrogen and oxygen enriched carbons were prepared by the cost-effective synthesis route of carbonization of
Low-cost carbon adsorbents polyacrylonitrile (PAN) and subsequent KOH activation for CO2 capture. The effect of four impregnation mass
High surface area ratios (KOH: PAN = 1–4) and activation temperatures (600–900 °C) on the synthesized carbon adsorbent
KOH activation properties was explored by different analyses. The X-ray photoelectron spectroscopy (XPS) revealed the ex-
CO2 capture
istence of basic nitrogen and oxygen functionalities on the adsorbent's surface which increases the adsorption
Isotherms
rate for CO2 by providing its basic sites. By increasing mass ratio (KOH:PAN) from 1:1 to 3:1, the surface area
Thermodynamic studies
increased from 1152.4 to 1884.2 m2 g−1 and the dynamic CO2 adsorption capacity also increased from 2.1 to
2.5 mmol g−1 respectively, at 30 °C (approximately ten times the adsorption capacity of untreated PAN,
0.22 mmol g−1). Physisorption and exothermic nature of the process were confirmed by the decrease in the
adsorption capacity of the adsorbents with the increase in adsorption temperature. Moreover, good cyclic sta-
bility and regenerability over 5 adsorption-desorption cycles were obtained for the adsorbents. The fractional
order kinetic and Temkin isotherm models fitted best with the adsorption data. A heterogeneous interaction
between CO2 and the surface of adsorbents was suggested by the isosteric heat of adsorption values. Combined
with the simple method for the preparation of activated carbon adsorbents, efficient CO2 adsorption and ex-
cellent regeneration make it appropriate adsorbents for post-combustion CO2 capture.

1. Introduction
The effect of CO2 emissions on global warming has been continuing
to increase, which is a serious threat to life on earth and also, re-
sponsible for the rapid climate change including the ocean acidification
(Petrescu et al., 2017) (Aljerf, 2016). The concentration of atmospheric
CO2 can come close to 570 ppm by the year 2100 (Singh et al., 2018a)
and that is very much greater than the preindustrial level of CO2 con-
centration (300 ppm) (Oh, 2010). Currently, the most promising and
practical strategy to reduce atmospheric CO2 concentration is carbon
dioxide capture and storage (CCS), where CO2 captured initially from
large CO2 point sources and then compressed and transported and lastly
stored (Shi et al., 2017). In the CCS, post-combustion technology is
generally used for CO2 adsorption due to its flexibility and ease of
retrofitting in the already existing coal-fired power plants (Lee et al.,
2012). It includes adsorption, membrane separation, cryogenic se-
paration, absorption, and biological fixation (Valiani et al., 2017).
Absorption using alkanoamines is mostly used by many researchers but
it has some drawbacks like energy penalty for the regeneration of the
absorbents, high corrosion, and oxidation-reduction of the used absor-
bent (Caskey et al., 2008). Among the different methods, adsorption via
porous solid materials (MOFs, zeolites, carbons, etc.) have many ad-
vantages like low energy requirement, high adsorption capacity, cost-
effective, the simplicity of use at different pressures and temperatures
with eco-friendly features as compared to others (Aljerf, 2018; Singh
et al., 2018a, 2018b).
Carbon-based materials are the most promising adsorbents than the
other solid adsorbents for CO2 adsorption because of its wide avail-
ability, low cost, high thermal stability, tunable porosity, high surface
area, low energy requirements and fast adsorption kinetics (Singh et al.,
2019b; Zhou et al., 2013). Moreover, activated carbons (AC) are best-
known adsorbents for the various environmental applications like
heavy metals removal and organic materials from the aqueous solutions
as well as purification and storage of the gases (Kazemi et al., 2016).
This is by a reason for its rare properties like high surface area along
with micropore volume and most importantly, surface chemistry which

∗
Corresponding author.
∗∗
Corresponding author.
E-mail addresses: jasminder.singh91@gmail.com (J. Singh), hbhunia@thapar.edu (H. Bhunia), soumen.basu@thapar.edu (S. Basu).

https://doi.org/10.1016/j.jenvman.2019.109457
Received 27 June 2018; Received in revised form 19 August 2019; Accepted 21 August 2019
0301-4797/ © 2019 Elsevier Ltd. All rights reserved.
J. Singh, et al. Journal of Environmental Management 250 (2019) 109457

has a greater influence on the CO2 adsorption capacity of the adsorbents Table 1
(Chiang and Juang, 2017). The simple and inexpensive process for the Adsorbents synthesized at different conditions.
development of ACs is one of the great challenges to increase its Adsorbents Carbonization temp. Activation temp. KOH:PAN
availability for large-scale applications. Therefore, many efforts have notation (°C) (°C) (weight)
been done for the production of ACs from inexpensive and novel pre-
P-600 600 – –
cursors to utilize in the different potential applications (González-
P-700 700 – –
García, 2018; Menya et al., 2018). Fundamentally, ACs can be prepared P-800 800 – –
by using two different activation methods: physical and chemical (Tran P-900 900 – –
et al., 2018). In the physical method, the precursors are pyrolyzed by P-1-800 800 800 1
using steam, CO2, and air, or a mixture of three which involves the P-2-800 800 800 2
P-3-800 800 800 3
carbon surface oxidation by CO2 or steam (Baek et al., 2016; Kong et al.,
P-4-800 800 800 4
2017). The production of CO2 and steam increases the cost of the P-3-600 800 600 3
treatment process (Rambabu et al., 2013). On the other side, chemical P-3-700 800 700 3
activation process is carried out by mixing the selected precursors with P-3-900 800 900 3
the desired mass ratio of activating agents such as KOH (de Souza et al.,
2013), K2CO3 (Adinata et al., 2007), NaOH (Byamba-Ochir et al.,
2016), H2SO4 (Mui et al., 2010), ZnCl2 (Olivares-Marín et al., 2006), PAN. After carbonization, stabilized P-800 was physically infused with
and then carbonized under inert atmosphere which produces the higher KOH at different weight ratios (KOH: PAN = 1–4). The resultant mix-
yield and development of porosity in the materials, by means of de- ture was kept for drying overnight at 120 °C followed by heating at
hydration along with degradation of precursor's structure. The activa- 600 °C to 900 °C using N2 flow (60 ml min−1) for 2 h (Al-Fatesh and
tion temperature, time and heating rate play an crucial role in Fakeeha, 2012). The activated carbons were then washed with 2 M HCl
achieving ACs with specific characteristics. Considering this point, ACs for the removal of K+ ions and distilled water to get the neutral pH
produced from different carbon precursors by using respective acti- value respectively (Boudia et al., 2019). Finally, the resulting carbons
vating agents (Laksaci et al., 2017) in which, KOH is widely applied and were dried in an oven for 15 h at 120 °C. The developed adsorbents are
preferred as compared to other activators due to its major role in the illustrated in Table 1 with preparation variables and sample notation.
improvement of specific surface area as well as porosity (produces wide
and narrow micropores) and hence increases the capability of CO2 3. Results and discussion
adsorption on the respective materials (González-García, 2018).
Kim et al. (2015) developed N-doped carbon adsorbents from 3.1. Material characteristic
polyacrylonitrile (PAN) by KOH activation which shows CO2 uptake of
1.02 mmol g−1 at adsorption temperature of 25 °C under 0.15 bar. Bai Fig. S1(a), supplementary information shows the N2 sorption iso-
et al. (2015) prepared KOH treated PAN fibers which show CO2 uptake therms of P-800 and different activated adsorbents. The sample, P-800
of 0.76 mmol g−1 under 1 bar pressure at 25 °C. Also, PAN activated (without activation) possesses a small volume of N2 adsorbed which
carbon fibers by using KOH as an activating agent, prepared by Shen signifies a negligible number of pores in it. On the other side, the KOH
et al. (2011) and they found CO2 adsorption capacity of 1.3 mmol g−1 activated samples show the typical type-I isotherm, which indicates the
at 25 °C. In literature, it has been seen that some of the modified carbon existence of microporosity in the samples. The existence of narrow
materials from PAN activation have good potential for CO2 capture but micropores as evident by the PSD curves (Fig. S1 b) are most suitable
the performance evaluation for the adsorbents are executed under the for CO2 trapping (Hao et al., 2010) and also, the presence of mesopores
static conditions which can't provide the real picture of CO2 separation (Table S1) permits CO2 molecules to diffuse on the adsorbent surface
from the flue gas application (Pevida et al., 2008) (Singh et al., 2019a). and therefore boost the adsorption rate (Yuan et al., 2016). By in-
Also, the synthesis processes are energy intensive and time-consuming creasing KOH impregnation ratios from 1:1 to 1:3, the values of (spe-
to enhance the porous properties of the adsorbents. Therefore, the aim cific surface area) SBET, (total pore volume) Vtotal and (micropore vo-
of the present study is to prepare the low-cost adsorbents from the most lume) Vmicro are increased from 1152.46 to 1884.2 m2 g−1, from 0.33 to
available N-rich precursor, PAN via simple and low-cost route for CO2 1.34 cm3 g−1 and from 0.17 to 0.92 cm3 g−1, respectively which im-
capture under dynamic conditions and in order to achieve this, PAN plies the formation of well-devolved porosity with the KOH activation.
was initially carbonized then activated with different mass ratios (1–4) This is due to the reactions (eqns. (S1)-(S5)) occurred during the KOH
of KOH which possessed a maximum CO2 adsorption capacity of activation with the carbon samples which indicate the formation of
2.5 mmol g−1 for P-3-800 at 30 °C. K2CO3, H2, and metallic K. The formation of metallic K into the matrix
of carbon widened the graphitic layered structures and generates the
2. Experimental pores which increase the surface area (Chiang and Juang, 2017). Also,
the removal of K compounds with HCl and water leads to develop the
2.1. Materials porosity in the samples (Xue and Shen, 2003). With the further incre-
ment in the impregnation ratio to 4:1 (KOH: PAN), the surface area
PAN with the volatile matter of 86.75% purchased from Indian (1694.4 m2 g−1) as well as total pore volume (0.96 cm3 g−1) decreases
Acrylics Ltd, India, and KOH obtained from Loba Chemie Pvt. Ltd, which may be due to the pore blockage and resistance in the devel-
India. Purified N2, CO2 gases (99.99%) and various gas mixtures of CO2 opment of pores within the PAN structure. The samples which are di-
(6%, 20% and 50%) were purchased from Sigma Gases and Services, rectly carbonized exhibits the negligible surface areas
India, for CO2 capture performances. (23.45–93.8 m2 g−1) and pore volume (0.06–0.31 cm3 g−1) values in
comparison to the other activated carbons. Overall, an increase in the
2.2. Synthesis textural properties with KOH activation and increasing impregnation
ratio indicating that the treatment route i.e. carbonization followed by
Firstly, PAN was carbonized in a horizontal tube furnace fitted with KOH activation shows significant role in the enhancement of porous
a quartz tube under N2 flow of 60 ml min−1 and the temperature was structure in the non-porous adsorbents.
set at 600–900 °C (heating rate- 10 °C min−1) for 2 h (Nar et al., 2016). Table S1 displays the elemental composition of the adsorbents
The obtained carbonized material at 800 °C was labeled as P-800 and which confirms the presence of nitrogen and oxygen heteroatoms. All of
preferred as a reference sample for the study, whereas, P denotes for samples are rich in carbon content (> 70%) except P-4-800. The

2
J. Singh, et al.
Fig. 1. SEM micrographs of (a) P-800 and (b) P-1-800 at 5 μm, (e) P-2-800, (f) P-3-800, and (i) P-4-800 at 10 μm; HRTEM images of (c) P-800, (d) P-1-800, (g) P-2-
800, (h) P-3-800, and (j) P-4-800 at 5 nm.
presence of carbon content in the adsorbent enhance the CO2 adsorp-
tion due to Van der Waals forces (Singh and Kumar, 2016). The sample,
P (PAN powder) shows higher nitrogen content (25.85%) but upon
changing the carbonization and activation conditions, a decrease in the
nitrogen content (16.7–2 wt%) was observed. This is due to the de-
composition and oxidation of the nitrogen species during chemical
activation. On the other side, the oxygen content increases from 13.1 to
38.54 wt% for the activated carbons due to the insertion of ‘O’ atoms in
the carbon framework with the KOH activation.
Details of SEM and TEM images of P-800, P-1-800, P-2-800, P-3-
800, and P-4-800 are shown in Fig. 1. The SEM image of the direct
carbonized sample, P-800 (Fig. 1a) shows the smooth surface without
any cracks or defects and pores whereas the porous surface of the KOH
activated samples can be observed in Fig. 1b, e, f and i. The small pits
and cracks distributed over the entire surface of the activated ad-
sorbents reveal that there are severe interactions between KOH and
PAN during the carbonization process. The impact of KOH activation on
the adsorbents leads to the conversion of non-porous to the porous
carbon surface, which increases the diffusion path for the entrapment of
CO2 molecules. Also, TEM images (Fig. 1d, g, h, and j) of KOH activated
samples shows the randomly oriented micropores. The non-porous and
graphitic like layer structure can be seen in sample P-800 (Fig. 1c),
whereas P-3-800 shows the larger micropore size (Fig. 1h) as compared
to other activated samples. Therefore, SEM and TEM analysis confirm
the development of porous surface morphology through KOH activation
which is beneficial for CO2 adsorption.
In order to know about the chemical bonding/states and functional
groups, the XPS analysis was performed for the adsorbents. The re-
spective binding energies, full width half maximum (FWHM) and re-
lative area (A%) for the deconvoluted peaks of the XPS spectra is illu-
strated in Table S2.
C1s spectra for all the samples are shown in Fig. 2a which are de-
convoluted into four components: the peaks at 284.39, 284.97, 285.85
3
Journal of Environmental Management 250 (2019) 109457
and 288.75 eV are ascribed to C–C (C1), C–H (C2), C]N (C3) and C]O
(C4) functional groups (Jagst, 2010; Yao et al., 2017), respectively. The
major contribution (26.48–39.0% area) for C1 indicates the graphiti-
zation character of the activated samples. For C4, % area sharply in-
creases (5.95%–21.65%) for sample P-800 to P-1-800, signifying the
increase of oxygen functional groups after KOH activation. The de-
convoluted XPS O1s peaks for all the samples provide the information
of the surface oxygen-containing groups as displayed in Fig. 2b. The
peaks at 531.2, 532.04, and 533.3 eV are ascribed to carbonyl, ketone
or lactone (O1), C–OH (O2) functional groups, ether oxygen atoms in
anhydrides and esters (O3) and O4 for oxygen in water, respectively
(Chiang et al., 2017; Tiwari et al., 2017a). The increase in the %area for
O1 (17.91–22.61%) from P-1-800 to P-4-800, indicates the increase in
the carbonyl, ketone or lactone functional groups by increasing the
KOH: PAN mass ratio which is responsible for surface basicity. Also, the
area% for O3 is maximum (31.46%) in P-3-800, which represents the
basic nature of this sample as compared to the others (Tiwari et al.,
2017b). The N1s spectra (Fig. S2) is deconvoluted into four different
peaks at 398.3, 399.7, 400.7 and 402.4 eV which are ascribed to pyr-
idinic nitrogen (N1), pyridonic/pyrrolic nitrogen (N2), quaternary ni-
trogen (N3) along with pyridine-N-oxide (N4) (Sevilla et al., 2011)
functional groups respectively. Although, it has been reported that all of
these three types of nitrogen species are beneficial for CO2 capture but
N2 and N3 have the strongest impacts towards CO2 adsorption (Shi
et al., 2017). The percentage of N2 and N3 in P-3-800 is higher as
compared to other activated samples (Table S2) whereas, the percen-
tage of N1 decreases (35.78–14.37%) with KOH weight ratio because
pyridine N structure destroyed with activation (Chiang et al., 2017).
Fig. S3 shows the TGA curves of carbon samples. All the samples
exhibited weight loss with the rise in temperature from ca. 30 to 100 °C
caused by the elimination of unwanted moisture. The second region for
weight loss is in between 500 and 800 °C because of the degradation of
oxygen and nitrogen functionalities exists in the adsorbents. The order
J. Singh, et al.
Fig. 2. XPS spectra of PAN samples: (a) C1s and (b) O1s.
for the weight loss follows: P-4-800 (38.10%) > P-2-800
(34.84%) > P-1-800 (25.84%) > P-3-800 (24.36%) > P-800
(9.34%). It was observed that P-3-800 is the most thermally stable
among all the activated carbon samples.
Fig. S4 shows the XRD patterns of the activated samples. The sam-
ples exhibits the diffraction peaks with the 2ϴ values at 25° and 43°
corresponds to the (002) and (100) planes, respectively. This shows the
presence of graphitic carbon in the activated samples (Liu et al., 2017).
3.2. CO2 capture performance
The CO2 uptake by the synthesized carbon adsorbents examined by
thermogravimetric analysis is presented in Fig. 3. The adsorbents pre-
pared by direct carbonization shows the adsorption capacities between
0.5 and 1.0 mmol g−1 in which PAN carbonized at 800 °C exhibit
maximum capacity as shown in Fig. 3a. Whereas, untreated PAN sample
exhibited the lowest adsorption capacity of 0.22 mmol g−1. It was no-
ticed that, when the temperature increased towards 800 °C from 600 °C,
the adsorption capacity increased from 0.57 to 1.0 mmol g−1 because of
Fig. 3. CO2 adsorption capacities for (a) without activated and (b) with KOH activated carbon adsorbents at 30 °C.
4
Journal of Environmental Management 250 (2019) 109457
the increase in VBET and Vtotal (Table S1). Beyond 800 °C, the sample
showed a lower adsorption capacity of 0.80 mmol g−1 (at 900 °C) due
to the decrease in surface area. The adsorbents show the following
order in terms of CO2 uptake: P-800 > P-900 > P-700 > P-600 > P.
Therefore, P-800 shows the highest CO2 adsorption capacity and thus it
is further used for KOH activation study.
CO2 adsorption capacities obtained at different activation times
(1–2.5 h) is shown in Fig. S5a, which confirms that the CO2 uptake
capacity varies with the change in activation time during synthesis. It
increases with the increase in activation time till 2 h but further de-
creases with time. Therefore, 2 h activation time was used for the
synthesis of adsorbents. Also, the effect of activation temperature
(600–900 °C) was studied during the synthesis of adsorbents at 2 h of
activation time (Fig. S5b). It was examined that CO2 adsorption capa-
city increased up to 800 °C and then it got decreased by increase in the
activation temperature. This is due to the small number of carbon atoms
reacts with KOH at lower activation temperature during carbonization
and exhibit negligible pores although, at higher activating temperature,
maximum carbon atoms are in contact with KOH and cause the
J. Singh, et al.
development of micro- and meso-pores. When the activation tempera-
ture was above 800 °C, the adsorption capacity decreases because of the
meso- and micro-pores gets blocked due to the collapse of the carbon
matrix. Similar kind of observations was noticed by Tiwari et al. (2018).
The influence of KOH activation can be observed in Fig. 3, re-
presenting the differences in the adsorption capacity of direct carbo-
nized and KOH activated samples. Fig. 3b reveals the efficient and rapid
CO2 adsorption on the carbons consists of four KOH: PAN impregnation
ratios (1:1 to 4:1). The complete adsorption of direct carbonized sam-
ples occurred at 180 min whereas; fast CO2 adsorption kinetics was
shown by KOH activated samples with the major CO2 uptake in a period
of ca. 4 min. This is due to the lack of pores in the carbonized samples as
suggested by the nitrogen adsorption and SEM analysis. On the other
side, CO2 uptake by KOH activated samples increased by increasing
KOH: PAN mass ratio up to 3 and then it started decreasing (Fig. 3b).
The maximum CO2 uptake (2.5 mmol g−1) was observed for P-3-800
sample due to its significantly higher surface area with larger micropore
volume which provides a greater area for the physisorption of CO2
molecules and thus increased the CO2 adsorption. In addition, more
contribution of functional groups like pyrrolic nitrogen, quaternary
nitrogen, carbonyl, ketone, ether, and alcohol in this sample increases
its basicity and hence, favorable for the adsorption of CO2 which is
Lewis acid. It was noticed that the capacity decreased from 2.5 to
1.7 mmol g−1 by increasing KOH: PAN mass ratio beyond 3 probably
may be due to the decrease in the SBET and micropore volume as well as
the carbon content (Table S1) and also, the absence of quaternary
groups (from Table S2) in this sample makes it less basic. Hence, it is
concluded that not only SBET and Vmicro influence the CO2 capture
performance of the solid adsorbents but also the existence of heteroa-
toms have a major role to enhance it.
The adsorption conditions during CO2 capture performance and
chemical activation of the adsorbents are the two major factors af-
fecting the adsorption capacity. Fig. 4 shows the effect of adsorption
temperature as well as CO2 concentration on the CO2 uptake of P-800
and P-3-800 adsorbents. The adsorption capacities of P-3-800 adsorbent
is much higher than P-800. The adsorption capacity for P-3-800 and P-
800 decreases from 2.5 to 0.8 mmol g−1 and 1.0 to 0.44 mmol g−1 re-
spectively, by increasing the adsorption temperature from 30 to 100 °C.
This decrease in the adsorption capacities of adsorbents by increasing
the adsorption temperature at different CO2 concentrations, suggests
the physisorption and exothermic nature of the process (Rashidi et al.,
2013). The result confirms that the favorable adsorption takes place at
lower temperatures. The CO2 uptake by P-800 and P-3-800 at different
adsorption temperatures was as follows: 30 > 50 > 75 > 100 °C. On
the other side, adsorption capacities were increased by an increase in
CO2 concentration from 6 to 100% for both the adsorbents. At 30 °C, the
Fig. 4. CO2 uptake by porous carbons at 30, 50, 75 and 100 °C under various CO2 concentration flow.
5
Journal of Environmental Management 250 (2019) 109457
adsorption capacity increased from 1.1 to 2.5 mmol g−1 by increasing
CO2 feed concentration from 6% to 100% whereas; at 100 °C, it in-
creases from 0.2 to 0.8 mmol g−1 (Fig. S6). This may be due to the
increase in driving force on the carbon surface by increasing the CO2
concentration which leads to increase the adsorption capacity. We ob-
served that the adsorbent was saturated in a small time (1–2 min) at a
higher temperature but it takes more than 10 min at 30 °C to get satu-
rated. This may be due to the rapid adsorption takes place at a higher
temperature which leads to the faster saturation of the sample and
decreases its binding strength with CO2 molecules (Singh and Kumar,
2016). Also, the surface energy and molecular diffusion on the ad-
sorbent surface increase with the adsorption temperature which makes
CO2 gas to be unstable and as a result, enhance the desorption process
(Tiwari et al., 2017b).
Easy regeneration and stability are the most important factors along
with good adsorption capacity of the selected adsorbent for CO2 capture
applications. As P-3-800 adsorbent possesses the highest CO2 adsorp-
tion capacity along with thermal stability among all the activated
samples, therefore the adsorbent durability is further tested via multiple
adsorption-desorption cycles (Fig. 5a). The sample, P-3-800 exhibits
stable adsorption capacity (2.5 mmol g −1) over five cycles of adsorp-
tion/desorption with not any loss in the efficiency. Also, desorption
occurred quickly by increasing the temperature towards 200 °C. The
required thermal energy for the desorption of CO2 after the adsorption
is ca.1.26 MJ per kg of CO2 (calculations are shown in SI). The CO2
uptake after five cycles was stable for the sample (P-3-800), which in-
dicate its good stability and regenerability. Thus, these adsorbents not
only possessed significant CO2 uptake but also have the ability to re-
generate over multiple cycles with no loss of adsorption performance.
The CO2 capture capacities by P-3-800 in the present work and the
other adsorbents which are reported in the literature are correlated in
Table 2. In literature, many researchers used the amine modified car-
bons but mostly amines have low oxidative stability and the corre-
sponding carbons require high regeneration temperature for desorption
(Marques et al., 2013; Min et al., 2018). Also, it has been seen that the
various activation methods for the modification of the adsorbents are
being used by different researchers for CO2 adsorption. Among them,
KOH is found to be one of the most effective activating agents to en-
hance the porous properties and adsorption capacity of the adsorbents.
After comparing the results with the findings of other studies, it is found
that the activated adsorbents synthesized in the present study show
superior adsorption capacities. Although there are some higher ad-
sorption capacities shown by the adsorbents in few literature cases, but
the performance evaluation was not conducted under the dynamic
condition which is not of practical significance. Therefore, it can be
concluded that the synthesized adsorbents are the good candidates for
J. Singh, et al. Journal of Environmental Management 250 (2019) 109457

Fig. 5. (a) Multi-cycles of adsorption-desorption on P-3-800 at 30 °C (CO2 concentration-100%) and (b) kinetic models fit to the experimental adsorption data of
adsorbents at 30 °C.

capturing CO2 from the flue gas of power plants. Table 3

Kinetic model parameters.
3.3. Adsorption kinetics Kinetic Model Parameters Sample

Under the operating conditions during CO2 adsorption, fast kinetics P-1-800 P-2-800 P-3-800 P-4-800

exhibited by the adsorbents represents its adsorption efficiency towards Pseudo-first -order k1 0.77 2.0 2.59 2.13
CO2. So, the adsorption kinetic study is a very essential part for the qe 2.0 2.34 2.40 1.66
adsorption process which provides the ability of the adsorbents effi- R2 0.98 0.96 0.98 0.96
ciency towards the high adsorbate flow and gives the information for Error % 15.88 10.05 5.45 18.13
Pseudo-second -order k2 0.47 0.59 2.05 2.33
predicting adsorption rates (Goel et al., 2015). In this present study,
qe 2.37 2.30 2.52 1.72
CO2 adsorption kinetics of the adsorbents was investigated by using R2 0.92 0.97 0.96 0.96
three kinetic models with the rate equations as discussed in SI. Error % 15.63 14.56 8.56 17.14
Fig. 5b shows the fitting of experimental values with the different Fractional-order kn 18.95 36.07 37.58 33.27
kinetic models. It has been observed that the kinetic data for the ad- qe 2.10 2.28 2.48 1.70
N 1.92 3.47 2.73 3.65
sorption process obeyed the fractional order kinetic model as compared M 2.63 3.67 1.40 2.64
to others on the basis of higher R2 values as well as from lower error% R2 0.98 0.99 0.99 0.99
values (Table 3). In a similar way, Fig. 6 illustrates the fitting of the Error % 7.98 3.55 4.87 3.41
kinetic models with the experimental data of P-3-800 at various tem-
peratures as well as CO2 concentrations. Pseudo-first-order as well
pseudo-second-order kinetic models show over- and under-estimated and adsorbent interaction, adsorption isotherm study has been carried
values corresponding to the experimental data with respect to time. out in this work. In this regard, CO2 experimental adsorption data were
While the fractional order kinetic model fitted best over the entire fitted to three standard isotherm models as explained in SI. The cal-
range of adsorption which can also be seen by higher R2 values along culated isotherm parameters for different models along with the R2
with lower error % values as illustrated in Table S3. values are summarized in Table 4. The higher R2 values proving that
the experimental data fitted best with the Temkin isotherm model in-
dicate the heterogeneity of the adsorbent surface. Whereas, the de-
3.4. Adsorption isotherm study
creasing KF value with the increase in the temperature and n > 1
suggests the favorable adsorption occurs at low temperature (Aljerf,
To predict the adsorption mechanism and know about the adsorbate

Table 2
Comparison of CO2 adsorption capacity of the different activated carbons.
Adsorbent Treatment method Experimental conditions CO2 uptake Refs.
(mmol g−1)
o
CO2 Temp ( C)
(vol. %)

Fly ash Chemical/KOH (700 °C) 100 25 0.6 Alhamed et al. (2015)
Carpet Chemical/KOH (800 °C) 100 25 1.9 Olivares-Marín and Maroto-Valer (2011)
Plastic waste Chemical/KOH (500 °C) 100 25 1.09 Arenillas et al. (2005)
Bagasse and rice husk Chemical/ZnCl2 (500 °C) 100 30 1.74 and 1.29 (Boonpoke et al., 2011)
Waste biomass Physical/Hydrothermal 100 25 1.45 Hao et al. (2013)
(800 °C)
Soybean Chemical/ZnCl2 (600 °C) then Physical/CO2 (800 °C) 15.4 30 0.93 Thote et al. (2010)
PAN activated carbon Chemical/KOH (850 °C) 100 25 1.3 Shen et al. (2011)
PAN fibres Chemical/KOH (750 °C) 100 25 0.76 Bai et al. (2015)
P-3-800 Chemical/KOH (800 °C) 50 30 2.0 Present study
P-3-800 Chemical/KOH (800 °C) 100 30 2.5 Present study

6
J. Singh, et al. Journal of Environmental Management 250 (2019) 109457

Fig. 6. Kinetic models fit to the experimental adsorption data of P-3-800.

Table 4 adsorbents for CO2 and suggesting the increase in the randomness at the
Isotherm parameters values. solid/gas interface.
Isotherm Parameters Temperature
Clausius-Clayperon equation is used to calculate Qst values for P-3-
Model 800 at different qe (Fig. 7b) which are in the range from 29.73 kJ mol−1
30 °C 50 °C 75 °C 100 °C to 41.61 kJ mol−1 with the average value of 34.04 kJ mol−1. The
−1
random change in the Qst values was observed by increasing the surface
Langmuir qm (mmol g ) 2.59 2.06 1.65 1.20
KL (atm−1) 10.85 5.36 2.24 1.73
coverage suggesting the heterogeneous nature of the adsorbent surface.
R2 0.93 0.92 0.96 0.94 In addition, Qst values of the adsorbent are much greater than the re-
Freundlich KF (mmol g−1 atm−1/n) 1.58 1.35 1.13 0.92 ported values (28.4–10.5 kJ mol−1) for different carbon adsorbents
n 3.0 2.14 2.09 1.07 (Hsu et al., 2010), suggesting relatively stronger affinity towards CO2.
R2 0.94 0.96 0.93 0.96
Temkin KT (atm−1) 165.82 74.92 38.19 33.62
b (kJ mol−1) 5.24 6.71 9.97 15.50
4. Conclusion
R2 0.99 0.97 0.99 0.98

High surface area carbon adsorbents were prepared by KOH acti-

2018). Fig. 7a represents the experimental data fitting with Temkin
model for P-3-800.
3.5. Thermodynamic studies
Gibbs free energy, ΔG 0 (kJ mol−1) estimated by using eqn. S13
whereas, standard enthalpy change, ΔH ° (kJ mol−1) as well as standard
entropy change (ΔS 0) (kJ mol−1 K−1) can be measured from van't Hoff
plot (Aljerf, 2018) using the eqn. S14. In addition, Clausius–Clapeyron
equation (Guo et al., 2006) was applied to calculate the isosteric heat of
adsorption, Qst (kJ mol−1) which is represented in eqn. S15.
The calculated values of the thermodynamic parameters are dis-
played in Table 5. The ΔH° value (−11.93 kJ mol−1) indicates that the
adsorption process is exothermic and also its value < −20 kJ mol−1
defines the physisorption nature (Goel et al., 2016). Also, the negative
values of ΔG° at all adsorption temperatures indicating that the process
is spontaneous and feasible (Aljerf, 2018). Whereas, ΔS° found to be
positive (0.031 kJ mol−1) which indicates the higher affinity of the
vation of carbonized PAN which exhibits CO2 sorption capacities are in
the range of 1.7–2.5 mmol g−1 at the adsorption temperature of 30 °C.
The SEM results show better surface properties for activated carbons as
compared to carbonized samples. The surface area, as well as total pore
volume of the adsorbents, was changed significantly by changing the
weight ratio of KOH to PAN. The adsorbent, P-3-800 showed the
maximum CO2 uptake (2.5 mmol g−1) in comparison to all the syn-
thesized adsorbents due to its higher porosity and basicity.
Regeneration study showed that the synthesized adsorbents desorbed
quickly after adsorption and it exhibits a stable adsorption capacity
after the five adsorption/desorption cycles. Fractional order kinetics
and Temkin isotherm models were fitted best with the adsorption data.
The heterogeneity of the carbon surface was suggested by higher Qst
values. The adsorption process was spontaneous, feasible and exo-
thermic confirmed by thermodynamic parameters. High surface area
and porosity of the prepared ACs combined with excellent dynamic CO2
adsorption capacities (> 1 mmol g−1) with good thermal stability, and
regenerablity make these adsorbents beneficial for CO2 capture at
ambient temperatures.

7
J. Singh, et al. Journal of Environmental Management 250 (2019) 109457

Fig. 7. (a) Experimental data fitting of P-3-800 with Temkin model and (b) Plot of Qst values against surface loading (qe) for CO2 adsorption on P-3-800.

Table 5 Activation mechanism and microstructure analyses. Microporous Mesoporous Mater.

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Chiang, Y.-C., Juang, R.-S., 2017. Surface modifications of carbonaceous materials for
The authors do not have any intellectual as well as a financial carbon dioxide adsorption: a review. J Taiwan Inst Chem E 71, 214–234.
de Souza, L.K., Wickramaratne, N.P., Ello, A.S., Costa, M.J., da Costa, C.E., Jaroniec, M.,
conflict of interests to declare.
2013. Enhancement of CO2 adsorption on phenolic resin-based mesoporous carbons
by KOH activation. Carbon 65, 334–340.
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